EP0112528B1 - Procédé pour la fabrication d'esters d'hydantoine - Google Patents

Procédé pour la fabrication d'esters d'hydantoine Download PDF

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Publication number
EP0112528B1
EP0112528B1 EP83112382A EP83112382A EP0112528B1 EP 0112528 B1 EP0112528 B1 EP 0112528B1 EP 83112382 A EP83112382 A EP 83112382A EP 83112382 A EP83112382 A EP 83112382A EP 0112528 B1 EP0112528 B1 EP 0112528B1
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EP
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Prior art keywords
val
carboxylic acids
carboxylic acid
process according
esters
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EP83112382A
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German (de)
English (en)
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EP0112528A2 (fr
EP0112528A3 (en
Inventor
Wilfried Dr. Zecher
Rudolf Dr. Merten
Willi Dr. Dünwald
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Bayer AG
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Bayer AG
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Priority to AT83112382T priority Critical patent/ATE33663T1/de
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Publication of EP0112528B1 publication Critical patent/EP0112528B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2855—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring

Definitions

  • the invention relates to a process for the preparation of polymers containing hydantoin rings by reacting carbodiimides containing acylurea end groups with ⁇ , ⁇ -unsaturated carboxylic acid derivatives, and to the further reaction of the resulting intermediates with carboxylic acids which contain at least one further reactive group.
  • Low molecular weight hydantoins can be used in the pharmaceutical sector and in the crop protection sector.
  • Polyhydantoins can be used, for example, as temperature-resistant plastics, in particular in the electrical insulation sector (for example FR-PS 1 484694).
  • EP-A 79 020 and 80 079 disclose processes for the preparation of compounds containing hydantoin rings by reacting a carbondiimide with derivatives of unsaturated carboxylic acids. It is known from EP-A-12 379 that pofyamide hydantoins can be obtained by reacting polyfunctional aminocarboxylic acid derivatives in the presence of compounds containing carboxyl groups. These methods can be further improved by the present invention.
  • the process according to the invention represents a considerable advance, especially on an industrial scale.
  • the process avoids difficult-to-stir, highly viscous intermediate stages and precipitations, by which working on a larger scale was hardly possible until then.
  • the process enables the easy production of such oligomeric hydantoins and polymeric hydantoine mixed condensates, which in use are characterized by improved properties, e.g. characterized by increased elasticity and aging resistance.
  • isocyanates partially substituted with acylurea groups which are reaction products of polyisocyanates and lactams, can be used. 0.5 to 0.005, preferably 0.2 to 0.02, mol of lactam are reacted per Val of isocyanate.
  • Suitable lactams are, for example, pyrrolidone, dodecane lactam, preferably caprolactam.
  • Aliphatic radicals with 2-12 C atoms, or an aryl radical such as phenyl, tolyl, diphenylmethane and diphenyl ether radicals are particularly preferred.
  • z is an integer from 2-4, preferably 2-3, particularly preferably 2.
  • the polyisocyanates e.g. B. to influence the molecular weight
  • monoisocyanates for.
  • methyl or phenyl isocyanate are mixed in amounts of about 0.1 to 10 mol%.
  • the carbodiimides according to the invention are produced from the acyl isocyanates mentioned, preferably using catalysts, at temperatures of 0-200 ° C., preferably from 20 to 90 ° C.
  • Suitable catalysts are, for example, phospholines, phospholine oxides, e.g. 3-methyl-1-phenylphospholine oxide, phospholine sulfides or organometallic compounds such as phenyllithium and diethyl zinc.
  • a technical mixture of 1-methyl-1-phospha-2- and 1-methyl-1-phospha-3-cyclopentene-1-oxide (methylphospholine oxide) is particularly preferably used as a catalyst.
  • the monoesters of maleic acid and fumaric acid are preferably used as derivatives of ⁇ , ⁇ -unsaturated carboxylic acids, e.g. Monoalkyl esters such as methyl, ethyl, isopropyl, undecyl, and also cyclohexyl, benzyl, allyl, propargyl and phenyl monofumaric acid esters and monomaleic acid esters.
  • Monoalkyl esters such as methyl, ethyl, isopropyl, undecyl, and also cyclohexyl, benzyl, allyl, propargyl and phenyl monofumaric acid esters and monomaleic acid esters.
  • portions of the derivatives of the ⁇ , ⁇ -unsaturated carboxylic acids can be mixtures or partially reacted mixtures of ⁇ , ⁇ -unsaturated cyclic dicarboxylic acid anhydrides and of hydroxy compounds, preferably aromatic hydroxy compounds (for example known from DE-OS 2 654 112) can be used.
  • Mixtures of maleic anhydride and, for example, phenol or o-, m- or p-cresols are preferably used in this embodiment of the process according to the invention.
  • Carboxylic acids or carboxylic acid derivatives according to the invention which still contain at least one group which is reactive with acyl ureas are, for.
  • Monocarboxylic acids such as formic acid and benzoic acid and monoglycine esters such as ethyl phenylaminoacetate are used.
  • carboxylic acids such as fumaric acid monoalkyl esters, e.g. B. fumaric acid monoethyl ester, particularly preferably trimellitic anhydride and bis- [methoxy-carbonylisopropylaminophenyl] methane or mixtures thereof.
  • Step a) of the process according to the invention is preferably carried out at 20-80 ° C, step b) preferably at -20 to 180 ° C and step c) preferably at 50-200 ° C.
  • the 5-position substituted hydantoins produced according to the invention can be identified by their IR spectrum (for example by the characteristic bands for hydantoins and esters).
  • the higher molecular weight hydantoins have solution viscosities of 50-100,000 mPas, preferably 100-10,000 mPas, determined on a 15% by weight solution in m-cresol 70 at 25 ° C.
  • the reaction according to the invention can be influenced by catalysts, as are mentioned, for example, in DE-OS 3 003 773.
  • amines for example 1,4-diazabicyclo (2,2,2) octane, triethylamine, N, N-bis (dimethylaminoethyl) methylamine, N, N-dimethylaniline, N-ethylmorpho, has proven to be particularly favorable lin and 4-dimethylamino-pyridine, of lactams such as caprolactam and pyrrolidone and of phenols such as phenol and o-, m-, or p-cresol.
  • the reaction according to the invention can be carried out in solvents which do not react under the reaction conditions or only form loose addition compounds.
  • Suitable solvents are: (halogen) hydrocarbon, phenols, alcohols, esters, lactones, lactams, ethers, nitriles, phosphoric acid amides, sulfoxides and sulfones, for example methylene chloride, carbon tetrachloride, tetrachloroethane, trichlorethylene, xylenes, o-dichlorobenzene, phenol, cresols, benzoic acid alkyl alcohols , dimethyl phthalate, butyrolactone, caprolactone, acetophenone, cyclohexanone, benzyl alcohol, ethylene glycol, Glykolmonoethyletheracetat, Diethylenylglykolmonoethylether, diethylene glycol dimethyl ether, dimethylformamide, N-methyl
  • Methylene chloride is preferably used as the solvent for the reaction of the polycarbodiimide.
  • a preferred embodiment is to use the carbodiimide e.g. in toluene and then add the methylene chloride before the reaction with the ⁇ , ⁇ -unsaturated carboxylic acids. The further condensation can then be carried out after adding higher boiling solvents such as e.g. Phenol, technical cresol mixtures, dimethylformamide and N-methylpyrrolidone, optionally with distillation of the methylene chloride and the other volatile solvent components.
  • higher boiling solvents such as e.g. Phenol, technical cresol mixtures, dimethylformamide and N-methylpyrrolidone, optionally with distillation of the methylene chloride and the other volatile solvent components.
  • the substituted isocyanate partially formed by the addition of lactams to isocyanates is first converted to the carbodiimide. Then the addition of the .alpha.,. Beta.-unsaturated carboxylic acid to this carbodiimide is carried out and subsequently or simultaneously, after the addition of the substituted carboxylic acid which is reactive with acylureas, condensation is carried out.
  • a further embodiment consists in using mixtures of isocyanates and lactams or mixtures of partially carbodiimidized isocyanates and lactams for the production of acylated carbodiimides.
  • the polymers according to the invention are distinguished by particular temperature resistance, elasticity and abrasion resistance and are e.g. suitable for the production of lacquers, wire sheets, foils and moldings. Their properties can be adjusted for different areas of application by adding fillers, pigments and low and high molecular components, e.g. for the production of lacquers and films by mixing and polyesters, polycarbamide esters and polyamideimides, can be varied within wide limits (see e.g. DE-OS 2 654 112).
  • a stable solution of the varied polycarbodiimide is obtained (this shows the JR band at 2150 cm- 1 which is characteristic of carbodiimides).
  • the mixture is then cooled to 40 ° C. and 200 g of phenol are added at this temperature and then 496 g of monomethyl maleate are added, partly with cooling.
  • a stable solution of a polyhydantoin ester substituted with acylurea end groups is obtained. 1480 g of a mixture of equal parts of phenol and an industrial cresol mixture are added to the solution.
  • the temperature is then raised to 180 ° C. over the course of about 6 hours, during which methylene chloride and also toluene distill off.
  • the mixture is interrupted at 90 ° C.
  • a solution of the polyhydantoin ester in toluene / methylene chloride / phenol is prepared in accordance with Example 1 and in the proportions given therein.
  • the mixture is then diluted with 1200 g of phenol / cresol, the temperature is raised to 60 ° C. and 79.6 g of bis- [methoxycarbonylisopropylamino-phenyl- (4) -] - methane are introduced at this temperature.
  • Example 1 a solution of the polyhydantoin methyl ester in toluene / methylene chloride / phenol is prepared in the proportions given there. Then 1100 g of phenol / cresol (1: 1) are added, heated to 100 ° C. and 28.8 g of fumaric acid monoethyl ester are added. The temperature is then raised to 180 ° C. over the course of about 4 hours, with the remaining methylene chloride and toluene distilling off. The mixture is then diluted with 1350 g of phenol / cresol and stirred at 180 ° C. for a further 6 hours. The polyhydantoin ester is obtained as a 33% clear brown solution. The viscosity ⁇ 25 is 38 400 mPas.
  • a sample of the hydantoin solution is spread on a test sheet and baked in 15 minutes each at 200 and 300 ° C to a clear elastic paint film.
  • a sample of the hydantoin solution is baked on a glass plate at 200 and 300 ° C to a clear, hard lacquer film.
  • Another sample is mixed in a ratio of 1: 1, based on the solids content, with a polyester made of terephthalic acid, glycerin and ethylene glycol, mixed with 1% by weight titanium tetrabutylate and baked on a test sheet at 200 and 300 ° C to form a clear, elastic paint film .
  • a sample of this solution is spread on a test sheet and baked in 15 minutes each at 200 and 300 ° C to a clear elastic paint film.
  • toluene 250 g of 4,4'-diisocyanato-diphenylmethane are heated to 90 ° C. with 11.3 g of caprolactam for 0.5 hours and reacted with 1 g of methylphospholine oxide as a catalyst at 40 to 50 ° C. to give the polycarbodiimide.
  • the mixture is then diluted with 340 g of methylene chloride and 50 g of phenol and 123.5 g of methyl maleate are added dropwise at 40 ° C. with cooling.
  • a stable solution of the substituted polyhydantoin is obtained (bands in the IR spectrum at 1715 and 1775 cm -1 , which are still unchanged even after the solution has been left to stand at room temperature for 17 hours).
  • the mixture After adding 290 g of phenol / cresol, the mixture is heated, 4.8 g of trimellitic anhydride and 10.0 g of bis- [methoxycarbonylisopropylamino-phenyl- (4) -] - methane are added at 60 ° C. and the temperature is at simultaneous distillation of the methylene chloride and toluene increased to 180 ° C.
  • the mixture is then diluted with 345 g of phenol / cresol and stirred at 180 for a further 4 hours.
  • the toluene is then distilled off in vacuo at 80 ° C. and the reaction mixture is stirred at 120 ° C. for 4 hours and at 130 ° C. for 2 hours.
  • a sample of the hydantoin solution is spread on a glass plate and baked in 15 minutes at 200 and 300 ° C to form a clear, elastic lacquer film.
  • the coating solution is diluted with cresol / xylene (2: 8) to a solids content of 27% and in a vertical oven of 4 m length at an oven temperature of 400 ° C on a Cu wire of 0.7 mm diameter up to a diameter increase of 40-50 applied 11 m.
  • a copper wire with excellent mechanical values is obtained in a wide driving range.
  • the maximum outer fiber elongation is 88%, the heat shock 260 ° C, the softening temperature 352 ° C (DIN 46453-10.2) and the scraping ability 41 strokes.
  • the lacquer solution is diluted with cresol / xylene (2: 8) to a solids content of 25%.
  • a Cu wire 0.7 mm in diameter coated in accordance with Example 1) has a coating speed of 14 m / min. a max. External fiber elongation of 88%, a heat shock of 260 ° C, a softening temperature of 414 ° C and a scrape resistance of 84 strokes.
  • a sample of this hydantoin solution is diluted with cresol / xylene (2: 8) to a solids content of 25%.
  • the painting carried out according to example 1) results in a painting speed of 14 m / min. an insulated Cu wire of 0.7 mm diameter with an elasticity of 88%, a heat shock of 260 ° C, a scraping strength of 84 strokes and a softening temperature of 414 ° C.
  • the hydantoin solution thus prepared is diluted to a solids content of 25% with cresol / xylene.
  • the painting according to Example 1 at 400 ° C and a painting speed of 18 m / min. on a 0.7 mm diameter copper wire results in an elasticity of 88%, a heat shock of 260 ° C, a scraping resistance of 58 strokes and a softening temperature of 407 ° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Claims (5)

1. Procédé de production de polymérisats contenant des noyaux d'hydantoïne, caractérisé en ce que
a) on fait réagir des polyisocyanates organiques coiffés avec 0,5 à 0,005 mole de lactames par valence d'isocyanate à des températures de -10 à +200°C pour former des carbodiimides,
b) on fait réagir ces carbodiimides, par équivalent, avec une valence d'ester ou d'amide d'un acide carboxylique à non-saturation α,β, de formule
Figure imgb0010
dans laquelle
R5 est un groupe -OR6 ou un groupe amino
Figure imgb0011
dans lesquels
RB, R7 et RB représentent indépendamment les uns des autres un groupe alkyle, cycloalkyle, alcé- nyle, alcynyle, aryle ou aralkyle et R7 et R8 représentent en outre l'hydrogène et
R3 et R4 représentent indépendamment l'un de l'autre l'hydrogène ou un groupe alkyle ou des mélanges de phénols ou de crésols avec l'anhydride d'acide maléique à une température de - 20 à 250 °C, éventuellement en présence d'un catalyseur pour former des (poly)-hydantoïnes, et
c) on fait réagir ces (poly)-hydantoïnes avec des acides carboxyliques ou des dérivés de ces acides qui contiennent au moins encore un autre groupe apte à réagir avec des acylurées, du groupe des composés comprenant des acides di- carboxyliques aliphatiques et aromatiques, des dérivés d'acides carboxyliques à non-saturation α,β, de formule I, des acides polycarboxyliques aliphatiques et aromatiques et leurs anhydrides ainsi que des esters de bisglycine, dans une proportion, par équivalent de groupes acylurée terminaux, d'une valence d'anhydride, d'une valence d'acide carboxylique, d'une valence d'ester de glycine et de 0,5 valence de dérivés d'acides carboxyliques à non-saturation a,p, à des températures de 0 à 400 °C.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise des esters monoalkyliques d'acide fumarique comme acides carboxyliques substitués avec un autre groupe fonctionnel.
3. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise des acides tricarboxyli- ques ou tétracarboxyliques ou leurs anhydrides comme acides carboxyliques substitués.
4. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise l'anhydride d'acide trimel- litique comme acide carboxylique substitué.
5. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise des esters de bisglycine comme acides carboxyliques substitués.
EP83112382A 1982-12-22 1983-12-09 Procédé pour la fabrication d'esters d'hydantoine Expired EP0112528B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83112382T ATE33663T1 (de) 1982-12-22 1983-12-09 Verfahren zur herstellung von hydantoinestern.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3247350 1982-12-22
DE19823247350 DE3247350A1 (de) 1982-12-22 1982-12-22 Verfahren zur herstellung von hydantoinestern

Publications (3)

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EP0112528A2 EP0112528A2 (fr) 1984-07-04
EP0112528A3 EP0112528A3 (en) 1985-08-28
EP0112528B1 true EP0112528B1 (fr) 1988-04-20

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EP83112382A Expired EP0112528B1 (fr) 1982-12-22 1983-12-09 Procédé pour la fabrication d'esters d'hydantoine

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US (1) US4517353A (fr)
EP (1) EP0112528B1 (fr)
JP (1) JPS59120630A (fr)
AT (1) ATE33663T1 (fr)
DE (2) DE3247350A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3713670A1 (de) * 1987-04-24 1988-11-17 Bayer Ag Verfahren zur herstellung von ueberzuegen mit hydantoin-strukturen durch umsetzung carbodiimidgruppen enthaltender verbindungen mit ungesaettigten carbonsaeuren
FR2864534B1 (fr) * 2003-12-24 2006-02-17 Rhodia Chimie Sa Synthese d'acylurees et composition comportant des acylurees
US9205383B2 (en) 2009-01-13 2015-12-08 Ams Technologies Int. (2012) Ltd Solvent and acid stable membranes, methods of manufacture thereof and methods of use thereof inter alia for separating metal ions from liquid process streams

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1570552C3 (de) * 1965-03-23 1975-03-13 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Polyhydantojnen
DE1906492B2 (de) * 1969-02-10 1980-07-31 Bayer Ag, 5090 Leverkusen Carbonsäure-Derivate enthaltende Hydantoine und Polyhydantoine
US3939122A (en) * 1973-04-11 1976-02-17 Bayer Aktiengesellschaft Process for the preparation of compounds which contain hydantoin rings
DE2404741C2 (de) * 1974-02-01 1985-07-04 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Folien, Überzügen und Formkörpern aus Polyhydantoinen bzw. Polyparabansäuren
DE2654112C2 (de) * 1976-11-29 1984-10-04 Bayer Ag, 5090 Leverkusen Polykondensate
DE2657560A1 (de) * 1976-12-18 1978-06-22 Bayer Ag Verfahren zur herstellung von hydantoinen
DE2758569A1 (de) * 1977-12-29 1979-07-05 Bayer Ag Hydantoine
US4289868A (en) * 1978-11-08 1981-09-15 Bayer Aktiengesellschaft Polyhydantoins from unsaturated carboxylic acids and polyiso(thio)cyanates
DE2854412A1 (de) * 1978-12-16 1980-06-26 Bayer Ag Beschichtungsmittel zur herstellung von hitzeresistenten ueberzuegen und filmen
US4448942A (en) * 1981-11-11 1984-05-15 Bayer Aktiengesellschaft Process for the production of hydantoins
US4465839A (en) * 1981-11-11 1984-08-14 Bayer Aktiengesellschaft Process for the production of hydantoins

Also Published As

Publication number Publication date
JPS59120630A (ja) 1984-07-12
DE3247350A1 (de) 1984-06-28
DE3376332D1 (en) 1988-05-26
EP0112528A2 (fr) 1984-07-04
EP0112528A3 (en) 1985-08-28
US4517353A (en) 1985-05-14
ATE33663T1 (de) 1988-05-15
JPH0455209B2 (fr) 1992-09-02

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